We report on the superconducting properties of epitaxial thin films Y/sub 1-x/Ca/sub x/Ba/sub 2/Cu/sub 3/O/sub 7-y/ with 0/spl les/x/spl les/0.2, grown on SrTiO/sub 3/ [001] by Pulsed Laser Deposition (PLD) technique. The partial substitution of Ca/sup 2+/ at the Y/sup 3+/site in YBCO leads to a monotonic decrease of the zero resistance critical temperature, T/sub c/. The oxygen stoichiometry is varied by means of post-deposition thermal treatment varying the oxygen partial pressure. The dependence of T/sub c/ on annealing oxygen pressure can be attributed to an overdoping effect and/or to a cation disorder.